Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

Gerlach, Martin; Kirschtowski, Sabine; Seidel‐Morgenstern, Andreas; Hamel, Christof

doi:10.1002/cite.201700162

Cited by 7 publications

(9 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore hydroesterification should be performed at low CO partial pressures. These results are in agreement with experimental finding which reported best yields at the comparatively low CO pressure of 5 bar …”

Section: Catalyst Inhibition By Excess Cosupporting

confidence: 94%

“…and a kinetic network model was suggested based on three elementary reactions of the cycle. In the presence of CO, isomerization rate was significantly inhibited and high product yields of desired esters could only be achieved at high temperature and low CO pressure . However a more elaborate and detailed mechanistic kinetic model is required to allow process control and optimization which can only be derived after a detailed study of all the reaction steps plus side reactions of the catalytic cycle.…”

Section: Introductionmentioning

confidence: 99%

“…The influence of the different polar and non‐polar solvents on the thermodynamics and kinetics of different reaction steps of the HE of long chain oleochemical substrates has never been studied before and allows the development of an accurate kinetic model at realistic conditions. This work eliminates model uncertainties and inconsistencies between kinetic experiments and previous computational studies on different chemical systems …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources

2019

View full text Add to dashboard Cite

The transformation of chemical production processes to a sustainable feedstock from renewable sources requires a careful assessment of current thermodynamic data, reaction mechanisms and kinetics. The Pd-catalyzed alkoxycarbonylation of the long chain olefin methyl 10-undecenoate (10-UME) from castor oil with methanol yields the building blocks for a renewable polyamide. The mechanism for the complex multi-step reaction cycle including active catalyst formation was elucidated. The experimental catalyst selectivity with 1,2-bis(di-tert-butylphos-phino-methyl)benzene (1,2-DTBPMB) as a ligand towards the desired linear diester product can be reproduced and rationalized. The mechanisms of possible side reactions and well as catalyst inhibition by carbon monoxide were also investigated. Solvent effects have an influence on reaction equilibria and transition barriers. These were considered in polar (methanol) and nonpolar (dodecane) media using implicit or mixed cluster/ continuum solvation models when explicit solvent coordination was critical.

show abstract

Section: Catalyst Inhibition By Excess Cosupporting

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources

2019

View full text Add to dashboard Cite

show abstract

“…Reductive amination experiments were conducted in a high-pressure, stainless-steel batch Parr reactor equipped with a glass stirrer, a gas supply system, a pressure regulator and a temperature controller [22,23]. For the standard experiments the composition of MeOH/dodecane = 99:1 wt %/wt % was chosen.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems

Kirschtowski

Kadar²,

Seidel‐Morgenstern

et al. 2020

Chemie Ingenieur Technik

Self Cite

View full text Add to dashboard Cite

This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made. Supporting Information available onlineThe homogenously rhodium-catalyzed reductive amination of 1-undecanal was performed in two different thermomorphic solvent systems with the ligand Xantphos. The influences of partial pressure, temperature, methanol and catalyst concentration on the reaction were investigated. Based on a network analysis a kinetic model was derived and successfully parametrized for all studied solvent systems. Simulation results were found to be in good agreement with the experiments and allow a further process development and optimization.

show abstract

“…The addition of MSA ensured longer catalyst lifetimes . Kinetic models were described by Seidel‐Morgenstern et al., an investigation of the phase equilibria was performed by Sadowski and Lemberg, and Engell and co‐workers carried out an optimization of the reaction parameters . The application of a TMS to the methoxycarbonylation of oleochemicals seems to be principally limited because of the cross‐contamination of the solvents in each other and the loss of catalyst activity with every run.…”

Section: Applicationsmentioning

confidence: 99%

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

Bianga

Künnemann

Gaide

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

Over the past 20 years, thermomorphic multiphase systems (TMS) have been used as a versatile and elegant strategy for the recovery and recycling of homogeneous transition‐metal catalysts, in both batch‐scale experiments and continuously operated processes. TMS ensure a homogeneous reaction in a monophasic reaction mixture at reaction temperature and the recovery of the homogeneous transition‐metal catalyst through liquid–liquid separation at a lower separation temperature. This is achieved by using at least two solvents, which have a highly temperature‐sensitive miscibility gap. The suitability of commercially available solvents makes this approach highly interesting from an industrial point of view. For the first time, herein, all studies in the area of TMS are reviewed, with the aim of providing a concise and integral representation of this approach for homogeneous catalyst recovery. In addition to the discussion of examples from the literature, the thermodynamic fundamentals of the temperature‐dependent miscibility of solvents are also presented. This review also gives key indicators to compare different TMS approaches, for instance. In this way, new solvent combinations and in‐depth research, as well as improvements to existing approaches, can be addressed and promoted.

show abstract

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

Cited by 7 publications

References 17 publications

Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources

Mechanism and Control of the Palladium‐Catalyzed Alkoxycarbonylation of Oleochemicals from Sustainable Sources

Kinetic Modeling of Rhodium‐Catalyzed Reductive Amination of Undecanal in Different Solvent Systems

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

Contact Info

Product

Resources

About